Ab Initio Prediction of Borophene As An Extraordinary Anode Material Exhibiting Ultrafast Directional Sodium Diffusion For Sodium-Based Batteries
Ab Initio Prediction of Borophene As An Extraordinary Anode Material Exhibiting Ultrafast Directional Sodium Diffusion For Sodium-Based Batteries
Ab Initio Prediction of Borophene As An Extraordinary Anode Material Exhibiting Ultrafast Directional Sodium Diffusion For Sodium-Based Batteries
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DOI 10.1007/s11434-016-1118-7 www.springer.com/scp
Received: 9 May 2016 / Revised: 1 June 2016 / Accepted: 2 June 2016 / Published online: 18 June 2016
Ó Science China Press and Springer-Verlag Berlin Heidelberg 2016
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Fig. 2 (Color online) a Snapshot from AIMD simulation of geometrical structure of borophene from top view and b side view, c evolution of
free energy for the borophene supercell during the simulation
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three routes are labeled as ‘‘valley diffusion’’ (V1–V2–V1), AIMD simulation was also performed to evaluate the
‘‘peak diffusion 1’’ (V1–P2–V1) and ‘‘peak diffusion 2’’ thermal stability of borophene after adsorbed with sodium
(V1–P1–V1). In ‘‘valley diffusion’’, sodium diffuses along atom. Similar with that of pure borophene, during the
the ‘‘valleys’’, while in ‘‘peak diffusion’’, sodium diffuses whole simulation time (3 ps), no broken bonds were
across the ‘‘peaks’’. Nudged elastic band (NEB) calculation observed and the fluctuation of the free energy of the
was employed here to obtain the energy profiles. 9, 19 and system was in a small range as shown in Fig. S2a (online).
21 images were set for ‘‘valley diffusion’’, ‘‘peak diffusion More interestingly, when we track the movement of
1’’ and ‘‘peak diffusion 2’’ according to the diffusion adsorbed sodium atom, it can be found that the sodium
lengths. The obtained energy profiles are shown in Fig. 4b. atom moved along the x-direction (valley direction) as
Both ‘‘peak diffusion 1’’ and ‘‘peak diffusion 2’’ show a shown in Fig. S2b (online). The simulation results indicate
relative higher energy barrier of 0.24 and 0.25 eV, that sodium atoms could diffuse along the valley direction
respectively, while ‘‘valley diffusion’’ exhibits an ultralow freely at 300 K. Similar behavior can not be observed
energy barrier of 0.0019 eV, which agree well with the along the y-direction (peak direction), which agree well
above calculations on binding energies at different sites. with the anisotropic diffusion property calculated above.
This anisotropic diffusion property has also been predicted The high diffusion energy barrier along the peak direction
for lithium atom [37], which shows that the diffusion could also effectively confine the sodium atoms in the
energy barrier along the valley direction is a bit higher valleys and prevent them from clustering.
(0.0026 eV) than sodium.
According to Eq. (2), the diffusivity of sodium along the 3.4 Electrochemical properties of sodium adsorbed
valley direction at room temperature (T = 300 K) is about borophene
104 times higher than those along the peak directions,
which means the diffusion of sodium on borophene is To study the adsorption behavior at higher sodium con-
strongly anisotropic and the diffusion along the peak centrations, six different Na/B ratios (x = 0.0667, 0.0833,
directions are nearly impossible when compared with val- 0.125, 0.167, 0.25 and 0.5) have been considered by
ley diffusion. The diffusion energy barrier for sodium in employing 5 9 3, 4 9 3, 4 9 2 and 3 9 2 supercells. For
other investigated sodium anode materials such as each Na/B ratio, the sodium atoms were adsorbed onto both
Na2Ti3O7 and Na3Sb are 0.19 and 0.21 eV [27, 28], cor- sides of borophene evenly, as shown in Fig. 5a–f. When
responding to diffusivities about more than 10-3 times the concentration of sodium increases, as shown in Fig. 5g,
lower that of the ‘‘valley diffusion’’ in borophene. When the absolute value of binding energy will decrease
compared with other 2D materials, the energy barrier of accordingly due to the repulsion of adjacent sodium atoms,
‘‘valley diffusion’’ is still ultralow and the diffusivity is one while all the binding energies could keep negative lower
to seven magnitudes higher, as listed in Table S1 (online). than -0.5 eV. Thus, at high sodium concentrations, bor-
This ultrahigh diffusivity along the valley direction indi- ophene can still exhibit a strong binding toward sodium.
cates an excellent rate capability when using as anode The charge transfer between the binding sodium and bor-
material in sodium-based batteries. ophene is shown in Fig. S3 (online). In all the
Fig. 4 (Color online) a Three considered diffusion routes for sodium on the surface of borophene. b The energy profiles for the considered
diffusion routes
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Fig. 5 (Color online) a–f The structures of NaxB with different sodium concentrations. g The binding energy of sodium on borophene with
different sodium concentrations
concentrations considered, the sodium atoms lose their both sides of sheet is shared, and the maximum concen-
electrons to borophene. When Na/B ratio reach 0.5, both tration will be reduced to half of the current estimation.
sides of borophene will be fully covered by the sodium, and The open-circuit voltage (OCV) can be estimated using
we regard this value to be the maximum capacity. The [38, 39]
calculated corresponding theoretical capacity of Na0.5B is ENax1 B ENax2 B þ ðx2 x1 ÞENa
as high as 1,218 mAh g–1, much higher than those reported OCV ; ð3Þ
ðx2 x1 Þe
in both experiments [9–11] and theoretical calculations
(listed in Table S1 online). The theoretical capacity of where ENax1 B ; ENax2 B and ENa are the energies of
borophene for sodium is a bit smaller than that for lithium Nax1 B, Nax2 B and metallic sodium, respectively. Figure 6a
[37] (Li0.75B, 1,860 mAh g–1), which is caused by the shows the OCV at various concentrations calculated using
larger atomic radius. In practice, the borophene sheet may Eq. (3). Similar with the absolute value of binding energy,
be not well separated. For stacked borophene, the Na on the OCV will decrease as the concentration of sodium
Fig. 6 (Color online) a The calculated voltage profile along the sodiation process. b The density of states (DOS) of borophene at different
sodium concentration. c The lattice parameters of borophene at different sodium concentration
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